U.S. patent number 4,481,314 [Application Number 06/509,112] was granted by the patent office on 1984-11-06 for infrared radiation absorbent anthraquinone derivatives in polyester compositions.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Mark Rule.
United States Patent |
4,481,314 |
Rule |
November 6, 1984 |
Infrared radiation absorbent anthraquinone derivatives in polyester
compositions
Abstract
Disclosed are novel anthraquinone compounds containing
tetra-p-phenylenediamine substituents, particularly useful in
molding type polyester compositions and possessing strong infrared
absorptivity. This property renders these compounds attractive as
additives for increasing the infrared energy absorptivity of
polyesters either from high intensity quartz lamps or from certain
laser systems. These compounds are particularly useful in bottle
polyester material for increasing the blow-mold parison reheat
rate, and in the printing of plastic articles with lasers.
Inventors: |
Rule; Mark (Kingsport, TN) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
24025311 |
Appl.
No.: |
06/509,112 |
Filed: |
June 29, 1983 |
Current U.S.
Class: |
524/88; 252/587;
430/944; 430/945; 524/156; 524/160; 524/199; 524/206; 524/207;
524/239; 524/242; 528/288; 528/292 |
Current CPC
Class: |
C08K
5/18 (20130101); C08K 5/18 (20130101); C08L
67/02 (20130101); Y10S 430/145 (20130101); Y10S
430/146 (20130101) |
Current International
Class: |
C08K
5/00 (20060101); C08K 5/18 (20060101); C08K
005/42 (); C08K 005/18 (); C09K 015/24 () |
Field of
Search: |
;524/156,160,199,206,207,239,242,88 ;562/461 ;564/427 ;528/292,288
;560/10,25,44,48 ;252/587 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Hoke; Veronica P.
Attorney, Agent or Firm: Spurrell; Donald W. Reece, III;
Daniel B.
Claims
I claim:
1. A polyester composition comprising linear thermoplastic
polyester containing from about 1 to about 20,000 ppm of one or a
mixture of infrared absorbent compounds comprising anthraquinone
having in the 1, 4, 5 and 8-positions diamino radicals
independently selected from those of the formula ##STR7## wherein
R.sup.6 and R.sup.7 are each selected independently from hydrogen,
straight or branched alkyl radicals, cycloalkyl radicals, and aryl
radicals, wherein said radicals are unsubstituted or substituted
with 1-3 radicals different from the parent radical and
independently selected from alkyl, cycloalkyl, aryl, alkoxy,
alkylamino, alkylsulfonyl, alkylsulfonylamino, alkanoylamino,
aroylamino, alkylthio, arylamino, amino, cycloalkylamino, alkanoyl,
alkoxycarbonyl, alkanoyloxy, aroyl, arylsulfonyl, CF.sub.3,
arylsulfamoyl, cyano, halogen, hydroxy, nitro, sulfamoyl,
alkylsulfamoyl, dialkylsulfamoyl, carbamoyl, alkylcarbamoyl,
dialkylcarbamoyl, SO.sub.3 M, OSO.sub.3 M, COOR.sup.8 wherein
R.sup.8 is H, lower alkyl or lower hydroxyalkyl, and wherein M is
H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4 +.
2. The composition of claim 1 containing a coloring amount of a dye
component comprising the copolymerized residue of one or a mixture
of dyes of the formula ##STR8## wherein: either or both of rings A
and B may contain in any position thereon one or two groups of the
formula ##STR9## R and R.sup.3 each is hydrogen, lower alkyl or
lower hydroxy alkyl; R.sup.1, R.sup.2, R.sup.4 and R.sup.5 each
represents hydrogen or 1-3 substituents independently selected from
lower alkyl, lower alkyl substituted with lower alkoxy, phenyl, Cl,
Br, or lower alkanoylamino, lower alkoxy, lower alkoxy substituted
with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino,
chlorine, bromine, amino, lower alkylamino, lower alkylamino
substituted with lower alkoxy, cyclohexyl, phenyl, Cl, Br, or lower
alkanoylamino, arylamino, arylthio, aroylamino, lower
alkylsulfonyl, lower alkylthio, lower alkanoylamino, and
cyclohexylamino, wherein X is --S-- or --NH--; n is 1 or 2; and m
is 0, 1, or 2.
3. The composition of claim 1 wherein the polyester has an I.V. of
from about 0.65 to about 0.8 and is prepared from an acid
component, comprised of terephthalic acid, isophthalic acid,
mixtures thereof, and up to about 30 mole % of one or a mixture of
modifying acids, and a diol component comprised of ethylene glycol,
1,4-cyclohexane diol, mixtures thereof, up to about 5 mole %
diethylene glycol, and up to about 25 mole % of one or a mixture of
other modifying diols.
4. The composition of claim 2 wherein the dye component is
1,5-bis(2-carboxyphenylthio)anthraquinone or
1,5-bis(o-carboxyanilino)anthraquinone or mixtures thereof, each
being present in a concentration of from about 1.0 part per million
to about 3.0 percent by weight of the polyester.
5. The composition of claim 1 wherein the polyester has an I.V. of
from about 0.65 to about 0.8, is prepared from at least about 90
mole percent terephthalic acid, and a diol component comprised of
at least about 90 mole percent ethylene glycol, up to about 10 mole
% 1,4-cyclohexanedimethanol, and up to about 5 mole % diethylene
glycol, and contains from about 2.0 to about 1500 ppm of one or a
mixture of the copolymerized dyes, and from about 10 to about 1,000
ppm of one or a mixture of the infrared absorbent compounds.
6. The composition of claim 1 wherein the polyester is prepared
from terephthalic acid and a diol component comprising ethylene
glycol, up to about 5 mole % of diethylene glycol, and up to about
5 mole % of 1,4-cyclohexanedimethanol based on total moles of diol,
and contains from about 20 to about 100 ppm of one or a mixture of
the infrared absorbent compounds wherein R.sup.6 and R.sup.7 are
either methyl or ethyl.
7. The composition of claim 2 wherein the polyester is prepared
from at least about 90 mole % terephthalic acid and a diol
component comprised of at least about 90 mole % ethylene glycol, up
to about 10 mole % 1,4-cyclohexanedimethanol, and up to about 5
mole % diethylene glycol, each dye is present in reacted form in a
concentration of from about 2.0 to about 1500 ppm, and wherein from
about 5 to about 200 ppm of copper phthalocyanine is admixed
therewith, said parts being per million parts of the polyester.
8. The composition of claim 2, wherein the dye component comprises
one or both of the dyes of the formulae ##STR10## wherein X, R and
R.sup.3 are as defined therein.
9. The composition of claim 1 wherein R.sup.6 and R.sup.7 are each
selected from alkyl of 1-10 carbons, cyclohexyl and phenyl, and the
infrared absorbent compound or mixture thereof is present in a
concentration of from about 10 to about 1,000 ppm.
10. An article formed from the composition of claim 1.
11. An article formed from the composition of claim 2.
12. A blow-molding, bottle parison formed from the composition of
anyone of claims 1-9, 13 and 14.
13. The composition of claim 2 wherein the polyester has an I.V. of
from about 0.65 to about 0.8, is prepared from at least about 90
mole percent terephthalic acid, and a diol component comprised of
at least about 90 mole percent ethylene glycol, up to about 10 mole
% 1,4-cyclohexanedimethanol, and up to about 5 mole % diethylene
glycol, and contains from about 2.0 to about 1500 ppm of one or a
mixture of the copolymerized dyes, and from about 10 to about 1,000
ppm of one or a mixture of the infrared absorbent compounds.
14. The composition of claim 2 wherein the polyester is prepared
from terephthalic acid and a diol component comprising ethylene
glycol, up to about 5 mole % of diethylene glycol, and up to about
5 mole % of 1,4-cyclohexanedimethanol based on total moles of diol,
and contains from about 20 to about 100 ppm of one or a mixture of
the infrared absorbent compounds wherein R.sup.6 and R.sup.7 are
either methyl or ethyl.
Description
DESCRIPTION
This invention concerns novel infrared radiation (hereinafter
termed infrared) absorbent compounds and polyester compositions and
articles containing the same. The present compounds blended or
copolymerized with polyesters increase the infrared absorbtivity
thereof from high intensity quartz lamps or certain laser systems.
The compounds are quite thermally stable and particularly useful,
for example, in bottle polyester for increasing the injection
molded, blow-molding bottle parison (blow-molding preform) reheat
rate, and in polyester articles to be printed with laser radiation.
The compounds are also fast to light and are not extractable from
the polyester, properties especially valuable in food applications
such s blow-molded beverage bottles and the like.
The novel infrared absorbent compounds of this invention comprise
anthraquinone having in the 1, 4, 5 and 8 positions diamino
substituents independently selected from those of the formula
##STR1## wherein R.sup.6 and R.sup.7 are each selected
independently from hydrogen, straight or branched alkyl radicals,
cycloalkyl radicals, and aryl radicals wherein said radicals are
unsubstituted or substituted with 1-3 radicals different from the
parent radical and independently selected from alkyl, cycloalkyl,
aryl, alkoxy, alkylamino, alkylsulfonyl, alkylsulfonylamino,
alkanoylamino, aroylamino, alkylthio, arylamino, amino,
cycloalkylamino, alkanoyl, alkoxycarbonyl, alkanoyloxy, aroyl,
arylsulfonyl, CF.sub.3, arylsulfamoyl, cyano, halogen, hydroxy,
nitro, sulfamoyl, alkylsulfamoyl, dialkylsulfamoyl, carbamoyl,
alkylcarbamoyl, dialkylcarbamoyl, SO.sub.3 M, OSO.sub.3 M, and
COOR.sup.8 wherein R.sup.8 is H, alkyl or hydroxyalkyl, M is
H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4.sup.+, and wherein the above
alkyl radicals and alkyl moieties (segments) of the other radicals
such as alkylamino are straight or branched chain of from 1-20
carbons, the cycloalkyl radicals or moieties have 4-8 ring carbons,
and the aryl radicals or moieties have 6-10 ring carbons. Preferred
for R.sup.6 and R.sup.7 are straight or branched alkyl of 1-10
carbons, cyclohexyl, or phenyl.
The following table gives exemplary compounds of the present
invention according to the general formula ##STR2## wherein the
various alkyl groups, e.g., C.sub.6 H.sub.13, can be singular but
typically are mixtures of isomers, and wherein a designation such
as C.sub.6 H.sub.12 -OC.sub.2 H.sub.5 means that the alkoxy (or
other substituent) is on the end carbon of the alkyl moiety.
__________________________________________________________________________
a b c d
__________________________________________________________________________
H CH.sub.3 H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2
H.sub.5 C.sub.2 H.sub.5 C.sub.4 H.sub.9 --n C.sub.4 H.sub.9 --n
C.sub.3 H.sub.7 --n C.sub.3 H.sub.7 --n C.sub.8 H.sub.17 C.sub.8
H.sub.17 C.sub.12 H.sub.25 C.sub.12 H.sub.25 Ph Ph C.sub.6 H.sub.11
C.sub.6 H.sub.11 CH.sub.2 CH.sub.2 CN CH.sub.2 CH.sub.2 CN CH.sub.2
--C.sub.6 H.sub.11 CH.sub.2 --C.sub.6 H.sub.11 C.sub.6 H.sub.12
--OC.sub.2 H.sub.5 C.sub.6 H.sub.12 --OC.sub.2 H.sub.5 CH.sub.2
--C.sub.6 H.sub.11 CH.sub.2 --C.sub.6 H.sub.11 C.sub.4 H.sub.8
--NHCH.sub.3 C.sub.4 H.sub.8 --NHCH.sub.3 CH.sub.2 --SO.sub.2
CH.sub.3 CH.sub.2 --SO.sub.2 CH.sub.3 C.sub.6 H.sub.12
--NHCOCH.sub.3 C.sub.6 H.sub.12 --NHCOCH.sub.3 CH.sub.2 CH.sub.2
--NHCOPh CH.sub.2 CH.sub.2 --NHCOPH CH.sub.2 NHPh CH.sub.2 NHPh
CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 NH.sub.2 CH.sub.2 CH.sub.2
NH.sub.2 C.sub.16 H.sub.33 C.sub.16 H.sub.33 CH.sub.2 NHC.sub.6
H.sub.11 CH.sub.2 NHC.sub.6 H.sub.11 C.sub.16 H.sub.33 C.sub.16
H.sub.33 CH.sub.2 CH.sub.2 COC.sub.2 H.sub.5 CH.sub.2 CH.sub.2
COC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 COOCH.sub.3 CH.sub.2 CH.sub.2
COOCH.sub.3 CH.sub.2 SO.sub.2 Ph CH.sub.2 SO.sub.2 Ph C.sub.6
H.sub.12 --CF.sub.3 C.sub.6 H.sub.12 --CF.sub.3 CH.sub.2
CHClCH.sub.2 Cl CH.sub.2 CHClCH.sub.2 Cl C.sub.6 H.sub.10 --p-Cl
C.sub.6 H.sub.10 --p-Cl CH.sub.2 CH.sub.2 --NO.sub.2 CH.sub.2
CH.sub.2 --NO.sub.2 C.sub.6 H.sub.10 --p-COOH CH.sub.3 CH.sub.2
SO.sub.2 NHCH.sub.3 CH.sub.2 SO.sub.2 NHCH.sub.3 CH.sub.2 CH.sub.2
SO.sub.2 N(C.sub.2 H.sub.5).su b.2 CH.sub.2 CH.sub.2 SO.sub.2
N(C.sub.2 H.sub.5).sub.2 CH.sub.2 CONHCH.sub.3 CH.sub.2
CONHCH.sub.3 CH.sub.2 CH.sub.2 CON(CH.sub.3).sub.2 CH.sub.2
CH.sub.2 CON(CH.sub.3).sub.2 2 CH.sub.2 --C.sub.6 H.sub.10
--p-COOCH.sub.3 CH.sub.2 --C.sub.6 H.sub.10 --p-COOCH.sub.3
CH.sub.3 CH.sub.3 CH.sub.2 --C.sub.6 H.sub.4 --p-NO.sub.2 CH.sub.2
--C.sub.6 H.sub.4 --p-NO.sub.2 C.sub.9 H.sub.19 C.sub.9 H.sub.19
__________________________________________________________________________
e f g h
__________________________________________________________________________
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5
C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.4 H.sub.9 --n C.sub.4 H.sub.9
--n CH.sub.3 CH.sub.3 C.sub.6 H.sub.11 C.sub.6 H.sub.11 C.sub.4
H.sub.9 C.sub.4 H.sub.9 C.sub.12 H.sub.25 C.sub.12 H.sub.25 C.sub.4
H.sub.9 C.sub.4 H.sub.9 C.sub.12 H.sub.25 C.sub.12 H.sub.25
CH.sub.2 CH.sub.2 CH.sub.2 Cl CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2
Cl C.sub.12 H.sub.25 C.sub.12 H.sub.25 CH.sub.2 CH.sub.2 CH.sub.2
Cl CH.sub.2 CH.sub.2 CH.sub.2 Cl CH.sub.2 CH.sub.2 NHSO.sub.2
CH.sub.3 CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3
C.sub.5 H.sub. 10 --SC.sub.3 H.sub.7 --n C.sub.5 H.sub.10
--SC.sub.3 H.sub.7 --n C.sub.6 H.sub.11 C.sub.6 H.sub.11 H CH.sub.3
H CH.sub.3 Ph Ph C.sub.6 H.sub.10 --p-CH.sub.3 C.sub.6 H.sub.10
--p-CH.sub.3 Ph--p-CH.sub.3 Ph--p-CH.sub.3 C.sub.6 H.sub.10 --p-Cl
C.sub.6 H.sub.10 --p-Cl CH.sub.3 OOCCH.sub.3 CH.sub.3 OOCCH.sub.3
C.sub.5 H.sub.10 --COPH C.sub.5 H.sub.10 --COPh CH.sub.2 SO.sub.2
NHPh CH.sub.2 SO.sub.2 NHPH CH.sub.2 CH.sub.2 CN CH.sub.2 CH.sub.2
CN C.sub.6 H.sub.4 --p-OCH.sub.3 C.sub.6 H.sub.4 --p-OCH.sub.3
C.sub.6 H.sub.4 --p-CN C.sub.6 H.sub.4 --p-CN C.sub.6 H.sub.4
--p-COOH C.sub.12 H.sub.25 CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2
CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2 C.sub.6 H.sub.10 --p-CONH.sub.2
C.sub.6 H.sub.10 --p-CONH.sub.2 C.sub.6 H.sub.4 --p-SO.sub.3 Na
C.sub.6 H.sub.4 --p-SO.sub.3 Na C.sub.6 H.sub.10 --p-OH C.sub.6
H.sub.10 --p-OH CH.sub.2 CH.sub.2 CH.sub.2 --OH CH.sub.2 CH.sub.2
CH.sub.2 --OH C.sub.6 H.sub.9 --o,p-di-Cl C.sub.6 H.sub.9
--o,p-di-Cl C.sub.6 H.sub.2 --o,m,p-tri-Cl C.sub.6 H.sub.2
--o,m,p-tri-Cl C.sub.4 H.sub.9 --n C.sub.4 H.sub.9 --n C.sub.6
H.sub.11 C.sub.6 H.sub.11
__________________________________________________________________________
These compounds generally possess a .lambda..sub.max in the region
of from about 300 to about 1000 nanometers, and in certain
instances in the region of about 780 nanometers (.epsilon.=20,000)
and a weaker absorption in the region of about 440 nanometers
(.epsilon.=5,000). These wavelengths are considered herein to be
sufficiently close to art recognized infrared wavelengths to be
termed infrared. These compounds or mixtures thereof are used in
concentrations of from 1-20,000 parts per million of polyester
(hereinafter ppm), preferably 10-1,000, and most preferably 20-100
ppm, and can be present in blended form or as an integral part of
the polyester resulting, for example, from reaction of -COOR.sup.8
groups with the ethylene glycol during esterification in the
polyester preparation. For such reactive compounds, it is preferred
that no more than two --COOR.sup.8 groups be present such that
excessive chain branching does not occur.
The present compounds are generally prepared, for example, by
refluxing 1,5-dichloro-4,8-dinitroanthraquinone or
1,4,5,8-tetrachloroanthraquinone with a p-phenylenediamine type
reactant in a high boiling solvent, such as ethylene glycol or
dimethylformamide. An inert atmosphere is preferred but not
necessary. Thus, 1,4,5,8-tetrakis(p-dimethylaminoanilino)
anthraquinone (TDAA) was prepared by reacting 1.0 g. of
1,5-dichloro-4,8-dinitroanthraquinone with 50 ml. of
N,N-dimethyl-p-phenylenediamine in 50 ml. of ethylene glycol at
reflux for five hours. The reaction product was isolated by
dilution of the reaction mixture with water followed by filtration,
and possessed a .lambda..sub.max of 783 nanometers
(.epsilon.=20,000). This compound, having a green color, was stable
and unchanged after heating for two hours at 285.degree. C. in
glycerol. The p-diethylaminoanilino derivative (TDEAA) was
similarly prepared and had essentially the same properties.
The present compounds can be added at any stage of the polyester
preparation or thereafter to the polyester by techniques well known
to the art. One such technique which was employed for the present
invention is as follows:
Ten milligrams of the above infrared absorbent compound TDAA was
solvent-coated onto 200 g of poly(ethylene terephthalate) (PET)
pellets having an inherent viscosity (I.V.) of 0.72, using a 50/50
by wt. mixture of PET pellets in methylene chloride. This product
was dried at 125.degree. C. under vacuum and molded into 50 mil
thick amorphous polyester disks at 265.degree. C. The disks were
light green in color and exhibited a 7% increase in heat absorption
rate under quartz lamp illumination relative to a control of
identical PET but containing no infrared absorbent compound. The
ultraviolet to visible absorption spectrum of the disks show that
this compound was unaffected by the thermal treatment.
Various colorants such as the condensable dyes of U.S. Pat. Nos.
4,359,570, 3,372,128; 3,278,486; 3,359,230; 3,424,708; and
1,841,674 are typically used in conjunction with the present
compounds in accordance with the present invention to give
polyester of varying colors such as green, amber, and blue. Dyes
particularly useful herein are those of said U.S. Pat. No.
4,359,570 having the general formula ##STR3## wherein: either or
both of rings A and B may contain in any position thereon one or
two groups of the formula ##STR4## R and R.sup.3 each is hydrogen,
lower alkyl or lower hydroxyalkyl; R.sup.1, R.sup.2, R.sup.4 and
R.sup.5 each represents hydrogen or 1-3 substituents independently
selected from lower alkyl, lower alkyl substituted with lower
alkoxy, phenyl, Cl, Br, or lower alkanoylamino, lower alkoxy, lower
alkoxy substituted with lower alkoxy, phenyl, Cl, Br, or lower
alkanoylamino, chlorine, bromine, amino, lower alkylamino, lower
alkylamino substituted with lower alkoxy, cyclohexyl, phenyl, Cl,
Br, or lower alkanoylamino, arylamino, arylthio, aroylamino, lower
alkylsulfonyl, lower alkylthio, lower alkanoylamino, and
cyclohexylamino, wherein each aryl moiety is 6-10 carbons and the
term "lower.revreaction. as used herein means 1-6 carbons; X is
--S--or --NH--; n is 1 or 2; and m is 0, 1, or 2.
The preferred dyes within the above definition are those in which
at least one --COOR or --COOR.sup.3 group is in the ortho position
on each benzene ring with respect to the --X--linkage, and the most
preferred dyes have the formulas ##STR5##
Brightly colored polyester compositions can be obtained by
copolymerization with from about 1 ppm up to about 3.0 wt. % of one
or more of the above dyes, and with 1-20,000 ppm of one or a
mixture of any of the present compounds, either blended with the
polyester or actually copolymerized therein, which compositions can
be blow-molded into bottles or molded or otherwise formed into
useful articles such as food packages. A large variety of colors
can be obtained with mixtures of the above dyes and also by mixing
therewith various pigments including carbon black, copper
phthalocyanine, and TiO.sub.2. Also, fillers and the like may be
admixed with the colored compositions to give certain effects
supplementary to the dyes.
The present polyester compositions are prepared, e.g., as
follows:
EXAMPLE 1
Copolymerizing the Dye and Present Compound Into The Polyester
145.5 Grams (0.75 mole) of dimethyl terephthalate,
89.0 grams (1.44 moles) of ethylene glycol,
32.8 grams (0.23 mole) of 1,4-cyclohexanedimethanol,
120.0 ppm of Ti catalyst as titanium tetraisopropoxide,
200.0 ppm of the yellow dye
1,5-bis(2-carboxyphenylthio)-anthraquinone, and
50 ppm of the present infrared absorbent compound A of the formula
##STR6## are added to a 500-ml. round-bottom flask fitted with a
stirrer, condensate take-off, and nitrogen inlet head. The flask
and contents are immersed in a Woods metal bath at approximately
170.degree. C. The temperature is raised to 195.degree. C. The
temperature is raised to 195.degree. C. and maintained for two
hours and twenty minutes while ester exchange and esterification of
the dimethyl terephthalate, ethylene glycol,
1,4-cyclohexanedimethanol,
1,5-bis(2-carboxyphenylthio)-anthraquinone, and compound A occurs.
During all of the above reactions, a nitrogen purge of
approximately two cubic feet/hour is maintained over the reactants.
The temperature is then raised to 285.degree. C., the melt placed
under 0.10 mm. vacuum and polycondensation carried out for 50
minutes.
The inherent viscosities (I.V.) of the polyesters herein are in
deciliters/gram and are determined according to ASTM D2857-70
procedure in a Wagner Viscometer of Lab Glass Inc. of Vineland,
N.J., having a 1/2 ml. capillary bulb, using a polymer
concentration of 0.5% by weight in 60/40, phenol/tetrachloroethane,
by weight. The procedure is carried out by heating the
polymer-solvent system at 120.degree. C. for 15 minutes, cooling
the solution to 25.degree. C. and measuring the time of flow at
25.degree. C. The I.V. is calculated from the equation ##EQU1##
wherein: {n}=Inherent viscosity at 25.degree. C. at a polymer
concentration of 0.50 g./100 ml. of solvent;
ln=Natural logarithm;
t.sub.s =Sample flow time;
t.sub.o =Solvent-blank flow time; and
C=Concentration of polymer in grams per 100 ml. of
solvent=0.50.
Exemplary of the wide variety of useful polyesters are those
prepared from major amounts of either 1,4-cyclohexanedimethanol or
ethylene glycol or mixtures thereof, and up to about 30 mole % of
one or a mixture of modifying diols such as 1,2-propanediol,
1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol,
1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,3-propanediol,
1,6-hexanediol, 2-ethylhexanediol, 1,2-cyclohexanediol,
1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,
1,3-cyclohexanedimethanol, and diols containing one or more oxygen
atoms in the chain, e.g., diethylene glycol, triethylene glycol,
dipropylene glycol or tripropylene glycol. In general, useful diols
contain 2 to 18, preferably 2 to 12 carbon atoms.
The acids used to form these various polyesters are selected from
one or more cyclic or acyclic dicarboxylic acids. The term "acid"
as used herein including the claims includes the anhydride or other
reactive species such as esters, i.e., dimethyl terephthalate or
the like. Preferred are major amounts of terephthalic or
isophthalic or mixtures thereof, and up to about 30 mole % of one
or a mixture of modifying acids such as hexahydroterephthalic,
tetrahydrophthalic, hexahydrophthalic, hexahydroisophthalic,
endomethylenetetrahydrophthalic, endoethylenetetrahydrophthalic,
hexachloroendomethylenetetrahydrophthalic, tetrabromophthalic,
succinic, glutaric, adipic, suberic, sebacic, decanedicarboxylic,
2,2,4-trimethyladipic, maleic, fumaric, itaconic, citraconic and
the like.
The polyesters can be produced according to conventional processes,
e.g., with a catalyst such as titanium added as titanium
tetraisopropoxide, with or without the introduction of an inert gas
stream, as solution condensation in a solvent, or as a melt
condensation at temperatures of up to about 250.degree. C., or
higher.
The anthraquinone dye components comprise coloring amounts, i.e.,
from about 1.0 to about 5,000 and preferably from about 2.0 to
about 1500 parts of each dye per million parts of polyester (ppm).
The colored compositions are broadly defined as linear
thermoplastic polyesters containing a coloring amount of the
residue of one or a mixture of the dyes within the above general
formula, and from 1 to 20,000 ppm of one or a mixture of the
present compounds. Preferred of these are the linear thermoplastic
polyesters having an I.V. of from about 0.65 to about 0.8, prepared
from at least about 90 mole percent terephthalic acid, and a diol
component comprised of at least about 90 mole percent ethylene
glycol, up to about 10 mole % 1,4-cyclohexanedimethanol and up to
about 5 mole % diethylene glycol, and containing from about 2.0 to
about 1500 ppm of one or a mixture of the above copolymerized dyes,
and from about 10 to about 1,000 ppm of one or a mixture of the
present infrared absorbent compounds.
An especially preferred polyester composition is prepared from
dimethyl terephthalate and a diol component comprising ethylene
glycol, up to about 5 mole % of diethylene glycol, and up to about
5 mole % of 1,4-cyclohexanedimethanol based on total moles of diol,
and contains from about 2.0 to about 1500 ppm of one or a mixture
of the above copolymerized dyes I and II, and from about 20 to
about 100 ppm of one or a mixture of the above compounds TDAA and
TDEAA.
The invention has been described in detail with a particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
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